Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/12—Unsaturated polyimide precursors
  • C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences

Definitions

• the present invention relates to new N, N ⁇ -disubstituted bis-maleimides containing in their structure a diorganopolysiloxane group. It also relates to a process for the preparation of said N, N ⁇ -bis-maleimides from maleic anhydride and from amines containing in their structure a diorganopolysiloxane group.
• N, N ⁇ -disubstituted bis-maleimides can be used in particular for the preparation of thermostable polyimides.
• linear polyimides or poly (amide-imide) containing in their structure a diorganopolysiloxane group which are produced by reaction between a dianhydride of tetracarboxylic acid or a monoanhydride of tricarboxylic acid with for example alpha, omega-bis (aminophenoxy alkyl) diorganopolysiloxanes.
• a dianhydride of tetracarboxylic acid or a monoanhydride of tricarboxylic acid with for example alpha, omega-bis (aminophenoxy alkyl) diorganopolysiloxanes.
• alpha, omega-bis (aminophenoxy alkyl) diorganopolysiloxanes we also know (cf.
• the object of the present invention consists of new N, N mal-disubstituted bis-maleimides containing in their structure a diorganopolysiloxane group and not comprising an Si-OC bond, characterized in that they essentially correspond to the general formula: in which : .
• X which is in the ortho, meta or para position with respect to the carbon atom of the benzene ring linked to nitrogen, represents a following atom or group: .
• the symbol x is an integer in the range from 2 to 8.
• the symbols y and z represent numbers, identical or different, whole or fractional, the sum of which lies in the range from 0 to 100.
• the present invention also relates to a process for the preparation of bis-maleimides of formula (I) according to which maleic anhydride is reacted, in the presence of a dehydrating agent, a tertiary amine, an organic diluent and a catalyst, on a diamine containing a diorganopolysiloxane group of formula: in which X, R1, R2, R3, R4, R5, x, y and z have the meanings given above.
• diamines (II) containing a diorganopolysiloxane group are compounds which are well known in the prior art. They are for example described in the British patent GB-B-1,062,418 and in the American patent US-A-4,395,527.
• a first method for the preparation of these diamines consists in making react a compound of formula where X has the meaning given above and M is an alkali or alkaline-earth metal, with a bis (haloalkyl) disiloxane of formula: where x has the value indicated above and Y is a chlorine, bromine or iodine atom, operating at a temperature between 20 ° and 200 ° C in the presence of a polar aprotic solvent.
• a second preparation method taught by these documents consists in copolymerizing a mole of diamine with a diorganodisiloxane group, prepared as indicated above, with an amount of one or more cyclic diorganopolysiloxanes capable of giving y moles of siloxy groups of formula: and / or z moles of siloxy groups of formula:
• reaction takes place at a temperature of between 80 ° and 250 °, again in the presence of a solvent and optionally an appropriate catalyst.
• Another way of preparing the diamines of formula (II), with y and / or z being equal to zero or different from zero, is to react on an ethylenically unsaturated compound of formula: in which X, which is in ortho, meta or para position with respect to the carbon atom of the benzene ring linked to nitrogen, and x have the meanings given above, an alpha, omega-bis (hydrogen) diorganopolysiloxane of formula: in which R1, R2, R3, R4, R5, y and z have the meanings given above.
• This hydrosilylation reaction is carried out by operating in bulk in the absence of solvent and using a platinum-based catalyst.
• alpha, omega-bis (hydrogen) diorganopolysiloxane used are products well known in the silicone industry and are, for some, commercially available. They are for example described in French patents FR-A1-2,486,952 and FR-A5-2,058,988.
• the ethylenically unsaturated amino substrate which is well suited to react with the alpha, omega-bis (hydrogen) diorganopolysiloxane consists in particular of a allyloxyaniline of formula:
• Maleic anhydride is used in amounts at least equal to one mole per NH2 function available; larger quantities are generally used which are of the order of 1.01 to 1.5 moles per NH2 function available.
• a lower carboxylic acid anhydride such as acetic anhydride is advantageously used in an amount at least equal to one mole per available NH2 function present in the diamine molecule of formula (II) used. Larger quantities are generally used which are of the order of 1.05 to 1.5 moles per NH2 function available.
• tertiary amines include trialkylamines as well as N, N-dialkylanilines in which the alkyl radicals have from 1 to 12 carbon atoms. Triethylamine and N, N-dimethylaniline are of advantageous use.
• the amounts of tertiary amine are generally between 0.05 and 0.8 moles per available NH
• the reaction is carried out in a liquid organic diluent under the operating conditions, practically between 20 ° and 100 ° at atmospheric pressure.
• a liquid organic diluent under the operating conditions, practically between 20 ° and 100 ° at atmospheric pressure.
• preference will be given to those which dissolve, under the temperature conditions adopted for the reaction and in the presence of the other constituents of the reaction mixture, the starting maleic anhydride.
• - hydrocarbons such as benzene, toluene, cyclohexane, - chlorinated derivatives such as chlorobenzene or methylene chloride, - cyclic or non-cyclic oxide ethers such as tetrahydrofuran, dioxane or ethyl ether, - dialkyl ketones such as acetone or methyl ethyl ketone.
• catalysts use may be made of a nickel derivative which is soluble in the liquid phase of the reaction mixture such as, for example, nickel salts of carboxylic acids, optionally hydrated, as well as the chelated forms of this metal. Acetate and acetylacetonate are particularly suitable. These catalysts are used in very small quantities, of the order of 0.5.10 ⁇ 3 to 5.10 ⁇ 3 moles per mole NH2 function available.
• one begins by reacting maleic anhydride and the diamine of formula (II) by operating in the diluent chosen at a temperature ranging from 30 ° to 100 ° C for a period ranging, depending on the temperature, from a few minutes to 1 hour. Then the dehydrating agent, the tertiary amine and finally the catalyst are added to the reaction medium, then the mixture is left to react under the temperature conditions adopted previously for a period ranging, depending on the temperature, from 1 hour to 3 hours. Generally, the reaction is terminated by addition of a non-solvent such as water, then the bis-maleimide of formula (I) prepared is isolated according to the usual methods.
• a non-solvent such as water
• the new bis-maleimides of general formula (I) can be used in the form of a mixture with one or more other compounds comprising imide groups to prepare thermostable polymers for molding or for impregnation which have advantageous mechanical properties.
• thermostable polymers with imide groups are in particular those which comprise the reaction product, at a temperature ranging from 50 ° C to 300 ° C, between: - (a) an N, N ⁇ -bis-maleimide containing a diorganopolysiloxane group of formula (I); - And (b) an N, N ⁇ -bis-maleimide or a combination of several bis-maleimides of formula: in which : . the symbols Z, which are identical or different, each represent H, CH3 or Cl; .
• the symbol A represents a divalent radical chosen from the group consisting of radicals: cyclohexylenes; phenylenes; 4-methyl-1,3-phenylene; 2-methyl-1,3-phenylene; 5-methyl-1,3-phenylene; 2,5-diethyl-3-methyl-1,4-phenylene; and the radicals of formula: in which B represents a simple valential link or a grouping: and the symbols T, which may be identical or different, each represent a hydrogen atom, a methyl, ethyl or isopropyl radical;
• bis-maleimides of formula (I) where the diorganopolysiloxane group contains a plurality of Si - phenyl or substituted Si - phenyl bonds.
• Suitable bis-maleimides of this type are those belonging to the following groups, classified in ascending order of preference: - bis-maleimides No. 2, 3 and 4; - bis-maleimides n ° 6, 7 and 8; - bis-maleimides n ° 10, 11 and 12.
• bis-maleimides belonging to these preferred groups those which are particularly suitable are the compounds in which the ratio: is at least 0.25.
• the ratio: is at least 0.25.
• bis-maleimides of formula (III) there may be mentioned in particular: - N, N ⁇ -metaphenylene-bis-maleimide, - N, N ⁇ -paraphenylene-bis-maleimide, - N, N ⁇ -4,4 ⁇ -diphenylmethane-bis-maleimide, - N, N ⁇ -4,4 ⁇ -diphenylether-bis-maleimide, - N, N ⁇ -4,4 ⁇ -diphenylsulphone-bis-maleimide, - N, N ⁇ -cyclohexylene-1,4-bis-maleimide, - N, N ⁇ -4,4 ⁇ -diphenyl-1,1 cyclohexane-bis-maleimide, - N, N ⁇ -4,4 ⁇ -2,2-diphenyl propane-bis-maleimide, - N, N ⁇ -4,4 ⁇ -triphenylmethane-bis-maleimide, - N, N ⁇ -methyl-2 phenylene-1,3-bis-
• N, N ⁇ is preferably used for the preparation of these thermostable polymers -4,4 ⁇ -diphenylmethane-bis-maleimide taken alone or as a mixture with N, N ⁇ -methyl-2 phenylene-1,3-bis-maleimide, N, N ⁇ -methyl-4 phenylene-1,3-bis- maleimide and / or N, N ⁇ -methyl-5-phenylene-1,3-bis-maleimide.
• the quantities of reactants (a) and (b) are chosen so as to have, by weight relative to the total weight of these constituents: - from 2 to 50% and, preferably, from 5 to 20% of bis-maleimide of formula (I), - And from 50 to 98% and, preferably, from 80 to 95% of bis-maleimide (s) of formula (III).
• the polymers containing the abovementioned imide groups can be prepared by direct heating of the reagent (a) and of the reagent (b) at least until a homogeneous liquid mixture is obtained.
• the temperature may vary depending on the physical state of the compounds present, but it is generally between 50 ° C. and 300 ° C. It is advantageous to bring and maintain the starting compounds in a state of intimate mixing before and during heating using for example good agitation.
• the preparation of the polymers can also be carried out by heating the mixture of reactants within an organic diluent which is liquid in at least part of the range 50 ° C - 250 ° C.
• organic diluent which is liquid in at least part of the range 50 ° C - 250 ° C.
• aromatic hydrocarbons such as xylenes and toluene
• halogenated hydrocarbons such as chlorobenzenes
• polar solvents such as dioxane, tetrahydrofuran and dibutyl oxide
• dimethylformamide dimethyl sulfoxide
• N-methylpyrrolidone dimethylacetamide
• methylglycol and methyl ethyl ketone dimethylformamide
• dimethyl sulfoxide such as N-methylpyrrolidone, dimethylacetamide, methylglycol and methyl ethyl ketone.
• Polymer solutions or suspensions can be used as they are for many uses; the polymers can also be isolated, for example by filtration, optionally after precipitation using an organic diluent miscible with the solvent used. In this context, it is advantageous to use a hydrocarbon whose boiling point does not notably exceed 120 ° C.
• polymers containing imide groups can vary to a large extent depending in particular on the exact nature of the reagents used, the proportions of reagents chosen and the precise temperature conditions adopted within the previously mentioned range.
• these can be hardened polymers, insoluble in the usual solvents such as for example the compounds mentioned in the preceding paragraph and which do not exhibit any significant softening below the temperature at which they begin to degrade.
• these polymers can also be in the form of prepolymers (P) which are soluble in polar organic solvents and which have a softening point at a temperature below 200 ° C. (in general this softening point is between 50 ° C. and 150 ° C).
• P prepolymers
• These prepolymers can be obtained in bulk by heating the mixture of reactants until a homogeneous or pasty product is obtained at a temperature generally between 50 ° and 180 ° C for a period which can range from a few minutes to a few hours. , this duration being all the shorter the higher the temperature adopted.
• the preparation of the prepolymers can also be carried out in suspension or in solution in a diluent which is liquid in at least part of the range 50 ° - 180 ° C.
• the prepolymers (P) can be used in the liquid mass state, a simple hot casting sufficient for the shaping and the production of molded objects. We can also, after cooling and grinding, use them in the form of powders which lend themselves remarkably to compression molding operations, possibly in the presence of fillers in the form of powders, spheres, granules, fibers or flakes. In the form of suspensions or solutions, the prepolymers (P) can be used for the production of coatings and intermediate prepreg articles, the reinforcement of which can be constituted by fibrous materials based on silicate or aluminum oxide or zirconium, carbon, graphite, boron, asbestos or glass. These prepolymers (P) can also be used for the production of cellular materials after incorporation of a blowing agent such as for example azodicarbonamide.
• a blowing agent such as for example azodicarbonamide.
• the prepolymers (P) can be hardened by heating to temperatures of the order of 300 ° C, generally between 150 ° and 250 ° C; additional shaping can be carried out during hardening, possibly under vacuum or under super-atmospheric pressure, these operations can also be consecutive.
• the polymers according to the invention interest the fields of industry which require materials endowed with good mechanical and electrical properties as well as a great chemical inertness at temperatures of 200 ° to 300 ° C.
• the prepreg articles can be used for the production of parts having various shapes and functions in many industries such as aeronautics. These pieces, called laminates, which can be pieces of revolution, are obtained by plating several layers of prepregs on a form or a support. Prepregs can also be used as reinforcements or as a means of repairing damaged parts.
• the reactor is then introduced into an oil bath preheated to 55 ° C., then the catalyst is added.
• the latter is the Karsted catalyst (complex based on elementary platinum and 1,3-divinyl-1,1,3,3-disiloxane ligands): it is in solution in toluene (concentration of 3.5% by weight ) and 120 microliters of this catalyst solution are introduced with a syringe; the ratio r (weight of elementary platinum engaged / weight of the reaction mass) is equal to 60.10 ⁇ 6.
• each vial is rinsed with 5 cm3 of acetone, which are then added to the reaction mass, kept stirring for another 15 minutes.
• reaction mixture is maintained at reflux with stirring for 2 hours 30 minutes. The temperature is then lowered to 20 ° C.
• the reaction mixture is diluted with 80 cm3 of ice water (5 ° C) with vigorous stirring and the oily product present is then extracted with 80 cm3 of ethyl acetate.
• the organic phase obtained is washed with three times 80 cm3 of water to reach pH6 in the washing waters, then dried for 2 hours over anhydrous sodium sulfate.
• the ethyl acetate is evaporated off from the organic phase by completing this operation under reduced pressure (about 70 Pa) at 60 ° C and 24.10 g are collected (ie a yield by weight of 95% by theory) of a viscous, brown-orange product, the NMR spectrum of which is in agreement with the structure of the desired bis-maleimide which was defined at the start of this example.
• the operating mode is the same as that described in Example 1, paragraph 1.1, except with regard to the following points: . 20 g (0.004 mole) of an alpha, omega-bis (hydrogen) diorganopolysiloxane of formula: whose molecular mass is of the order of 4982 g; . 50 microliters of the catalyst solution are used; the ratio r (weight of elementary platinum / weight of the reaction mass) is equal to 64.10 ⁇ 6; . 1.2 g (0.008 mole) of metallyloxyaniline are poured into the reactor over 45 minutes and the mixture is returned to ambient temperature 30 minutes after the end of the pouring of this reagent.
• the product obtained with a weight of 21.1 g, is a viscous, orange oil, presenting a spectrum of RNM of the proton in agreement with the structure: and having a molecular mass of the order of 5280 g.
• the conversion rate of the reactants used is 100% (by NMR and infrared analysis, neither amine nor hydrogenated siloxane oligomer is detected) and the desired yield by weight of diamine is 100 %.
• the operating mode is the same as that described in Example 1, paragraph 1.2., Except as regards the following points: . 15 cm3 of a solution in acetone of 21 g (0.004 mole and 0.008 NH2 function) of the diamine siloxane prepared in paragraph 2.1 are poured in and 3 cm3 of a solution in acetone of 0.89 g (0.009) mole) of maleic anhydride; . 1.06 g (0.0104 mole) of acetic anhydride and 0.273 g (0.0027 mole) of triethylamine are then poured in, and then 40 microliters of the nickel acetate solution are added.
• the operating mode is the same as that described in Example 1, paragraph 1.1, except with regard to the following points: . 105 g (0.07 mol) of an alpha, omega-bis (hydrogen) diorganopolysiloxane of formula: whose molecular mass is of the order of 1492 g; . 350 microliters of the catalyst solution are used; the ratio r (weight of elementary platinum / weight of the reaction mass) is equal to 75.10 ⁇ 6; . 21 g (0.14 mol) of metaallyloxyaniline are poured into the reactor over 50 minutes and the mixture is returned to ambient temperature 30 minutes after the end of the pouring of this reagent.
• the product obtained weighing 125.3 g, is a viscous, brown oil, exhibiting a proton NMR spectrum in accordance with the structure: and having a molecular weight of the order of 1790 g.
• the conversion rate of the reagents used is 100% (by NMR and infrared analysis; neither amine nor hydrogenated siloxane oligomer is detected) and the yield by weight of desired diamine is 100 %.
• the operating mode is the same as that described in example 1, paragraph 1.2, except with regard to the following points: . 50 cm3 of an acetone solution of 65 g are poured (0.036 mole and 0.072 NH2 function) of the diamine siloxane prepared in paragraph 3.1 above and 20 cm3 of a solution in acetone of 7.8 g (0.079 mole) of maleic anhydride; . 9.6 g (0.094 mole) of acetic anhydride and 2.45 g (0.024 mole) of triethylamine are then poured in, and then 0.5 cm3 of the nickel acetate solution is added.
• the operating mode is the same as that described in Example 1, paragraph 1.1, except with regard to the following points: . 312 g (0.46 mole) of alpha, omega-bis (hydrogen) diorganopolysiloxane of formula: whose molecular mass is of the order of 678 g; . 1.49 cm3 of the catalyst solution is used; the ratio r (weight of elementary platinum / weight of the reaction mass) is equal to 91.10 ⁇ 6; . 137 g (0.92 mole) of metaallyloxyaniline are poured into the reactor over 60 minutes and the mixture is returned to ambient temperature 30 minutes after the end of the pouring of this reagent.
• the product obtained weighing 448.9 g, is a viscous oil orange-brown, with a proton NMR spectrum in agreement with the structure: and having a molecular mass of the order of 976 g. Under these conditions, the conversion rate of the reagents used is 100% (by NMR and infrared analysis; neither amine nor hydrogenated siloxane oligomer is detected) and the yield by weight of desired diamine is 100 %.
• the operating mode is the same as that described in example 1, paragraph 1.2, except with regard to the following points: . 20 cm3 of a solution in acetone of 25 g (0.025 mol and 0.050 NHtreatment function) of the diamine siloxane prepared in the preceding paragraph 4.2 are poured in and 25 cm3 of a solution in acetone of 6.4 g (0.055) mole) of maleic anhydride; . 6.1 g (0.06 mole) of acetic anhydride and 1.67 g (0.0165 mole) of triethylamine are then poured in, then 0.3 cm3 of the nickel acetate solution is added.
• thermostable polymer Preparation of a thermostable polymer.
• reaction mass which is limpid in appearance, is then poured into a mold preheated to 150 ° C. in order to prepare plates of dimension 140 x 100 x 4 mm which will undergo the following cooking cycle: . 10 minutes at 160 ° C, . 130 minutes between 160 ° and 250 ° C, . 16 hours at 250 ° C, . and 2 hours between 250 ° C and 25 ° C.
• the plates based on hardened, brown and translucent polymer are cut so as to obtain test pieces of dimensions 60 x 10 x 4 mm on which CHARPY impact tests are not notched according to standard NFT 51035. Resilience at 25 ° C thus obtained is 3.4 kJ / m2.
• the baking cycle for molded plates at 200 ° C is as follows: . 1 hour 45 minutes at 200 ° C, . 1 hour between 200 ° and 250 ° C, . 16 hours at 250 ° C, . and 2 hours between 250 ° C and 25 ° C
• the resilience at 25 ° C, measured on the test pieces, is 1.7 kJ / m2.

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